CN112429884A - Method for treating alkaline zinc-nickel alloy electroplating wastewater - Google Patents
Method for treating alkaline zinc-nickel alloy electroplating wastewater Download PDFInfo
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- 238000009713 electroplating Methods 0.000 title claims abstract description 121
- 239000002351 wastewater Substances 0.000 title claims abstract description 112
- 238000000034 method Methods 0.000 title claims abstract description 58
- QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical compound [Ni].[Zn] QELJHCBNGDEXLD-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 229910000990 Ni alloy Inorganic materials 0.000 title claims abstract description 24
- 229910001453 nickel ion Inorganic materials 0.000 claims abstract description 45
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims abstract description 44
- 238000005342 ion exchange Methods 0.000 claims abstract description 30
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000002253 acid Substances 0.000 claims abstract description 18
- 238000002156 mixing Methods 0.000 claims abstract description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 66
- 230000008929 regeneration Effects 0.000 claims description 30
- 238000011069 regeneration method Methods 0.000 claims description 30
- 239000011347 resin Substances 0.000 claims description 22
- 229920005989 resin Polymers 0.000 claims description 22
- 239000010802 sludge Substances 0.000 claims description 19
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 18
- 239000003729 cation exchange resin Substances 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 13
- 230000003472 neutralizing effect Effects 0.000 claims description 12
- 238000001556 precipitation Methods 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 238000007599 discharging Methods 0.000 claims description 9
- 238000006386 neutralization reaction Methods 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- 238000001514 detection method Methods 0.000 claims description 3
- 230000001172 regenerating effect Effects 0.000 claims description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 abstract description 18
- 239000008139 complexing agent Substances 0.000 abstract description 18
- 239000000243 solution Substances 0.000 description 63
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 33
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- 238000010521 absorption reaction Methods 0.000 description 13
- 239000000523 sample Substances 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 238000001179 sorption measurement Methods 0.000 description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 8
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 8
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 8
- 229910052759 nickel Inorganic materials 0.000 description 8
- 238000004448 titration Methods 0.000 description 8
- 229910052725 zinc Inorganic materials 0.000 description 8
- 239000011701 zinc Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 230000008901 benefit Effects 0.000 description 5
- 239000003344 environmental pollutant Substances 0.000 description 5
- 231100000719 pollutant Toxicity 0.000 description 5
- 230000001376 precipitating effect Effects 0.000 description 5
- 239000003513 alkali Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 4
- 235000017557 sodium bicarbonate Nutrition 0.000 description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 description 4
- 230000002411 adverse Effects 0.000 description 3
- 230000000536 complexating effect Effects 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 229910001431 copper ion Inorganic materials 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000012488 sample solution Substances 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- JMXROTHPANUTOJ-UHFFFAOYSA-H naphthol green b Chemical compound [Na+].[Na+].[Na+].[Fe+3].C1=C(S([O-])(=O)=O)C=CC2=C(N=O)C([O-])=CC=C21.C1=C(S([O-])(=O)=O)C=CC2=C(N=O)C([O-])=CC=C21.C1=C(S([O-])(=O)=O)C=CC2=C(N=O)C([O-])=CC=C21 JMXROTHPANUTOJ-UHFFFAOYSA-H 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- XHCCWBJFZUXJBV-UHFFFAOYSA-K trisodium 2-[(2-oxido-5-sulfophenyl)diazenyl]-3,6-disulfonaphthalene-1,8-diolate Chemical compound C1=CC(=C(C=C1S(=O)(=O)O)N=NC2=C(C3=C(C=C(C=C3C=C2S(=O)(=O)O)S(=O)(=O)O)[O-])[O-])[O-].[Na+].[Na+].[Na+] XHCCWBJFZUXJBV-UHFFFAOYSA-K 0.000 description 1
- SWGJCIMEBVHMTA-UHFFFAOYSA-K trisodium;6-oxido-4-sulfo-5-[(4-sulfonatonaphthalen-1-yl)diazenyl]naphthalene-2-sulfonate Chemical compound [Na+].[Na+].[Na+].C1=CC=C2C(N=NC3=C4C(=CC(=CC4=CC=C3O)S([O-])(=O)=O)S([O-])(=O)=O)=CC=C(S([O-])(=O)=O)C2=C1 SWGJCIMEBVHMTA-UHFFFAOYSA-K 0.000 description 1
- 210000003462 vein Anatomy 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5272—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using specific organic precipitants
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
- C02F1/62—Heavy metal compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/16—Nature of the water, waste water, sewage or sludge to be treated from metallurgical processes, i.e. from the production, refining or treatment of metals, e.g. galvanic wastes
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- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Treatment Of Water By Ion Exchange (AREA)
Abstract
The invention provides a method for treating alkaline zinc-nickel alloy electroplating wastewater, which comprises the following steps: (1) mixing the acid solution with the electroplating wastewater, and adjusting the pH of the electroplating wastewater to be less than or equal to 2.5; (2) and (2) removing zinc ions and nickel ions in the electroplating wastewater obtained in the step (1) by using an ion exchange method. The treatment method provided by the invention simplifies the treatment process, improves the treatment speed, reduces the treatment cost, and is particularly suitable for treating electroplating wastewater rich in EDTA complexing agent.
Description
Technical Field
The invention belongs to the technical field of sewage treatment, relates to a treatment method of electroplating wastewater, and particularly relates to a treatment method of alkaline zinc-nickel alloy electroplating wastewater.
Background
Along with the continuous enlargement of the scale of the current domestic electroplating industry, the treatment capacity and the treatment difficulty of electroplating wastewater are gradually increased. As one of the main sources of heavy metal wastewater, the environmental protection and harmless treatment of electroplating wastewater are problems facing the general needs of the electroplating industry.
Aiming at the traditional treatment process of the zinc-nickel alloy electroplating wastewater, the traditional treatment process mainly comprises the following three steps: (1) dilution and precipitation method: the method utilizes the advantage of larger water amount of other wastewater in the plant area to dilute the high-concentration solution for precipitation, but the treatment capacity is limited by the water amount of other wastewater in the plant area. (2) Chelating precipitation method: in the method, the copper ions in the wastewater are removed by adding sulfide or a polymer chelating agent, but the dosage of the medicament is influenced by the concentration of the complexing agent in the wastewater, and the dosage is large, so that the effluent is unstable. (3) Oxidation, breaking of the network and precipitation: the complexing agent is sufficiently oxidized and broken by using the oxidant, and the solution is adjusted to be alkaline to form hydroxide precipitate, however, under the condition of higher content of the complexing agent, a large amount of oxidant needs to be consumed, the treatment cost is higher, and the process is more complicated.
CN 109516602A discloses a method for treating zinc-nickel electroplating wastewater, which comprises the steps of carrying out primary precipitation, high-iron complex breaking agent treatment, high-molecular heavy metal catching agent treatment and flocculation precipitation on the zinc-nickel electroplating wastewater in sequence, and then discharging the zinc-nickel electroplating wastewater after reaching the standard. The method has the advantages of simple process flow, easy management and operation, high treatment efficiency and good vein breaking effect, and can treat the high-concentration zinc-nickel wastewater to be below 0.1mg/L at one time. However, under the condition of high complexing agent content, especially for electroplating wastewater rich in EDTA complexing agent, the treatment cost is increased by using a large amount of high-iron complexing agent.
CN 110980866A discloses a method for deeply removing zinc-nickel alloy electroplating wastewater, which comprises the steps of adjusting the pH value of the zinc-nickel alloy electroplating wastewater to 9-11, precipitating to remove ionic nickel and zinc, passing through an adsorption column filled with functional adsorption materials, and performing two-stage series concurrent adsorption, wherein one-stage adsorption mainly removes organic matters complexed with nickel and zinc in the wastewater, and the second-stage adsorption mainly removes residual nickel and zinc in the wastewater. However, the invention needs two stages of adsorption columns, which not only increases the complexity of operation, but also is not beneficial to saving the treatment cost.
CN 103241803A discloses an electroplating wastewater separation process, which comprises the following steps: (1) pre-filtering the electroplating wastewater to remove suspended impurities; (2) removing copper ions in the electroplating wastewater by passing the pre-filtered electroplating wastewater through copper-specific resin; (3) and (3) passing the electroplating wastewater obtained in the step (2) through cation exchange resin to remove nickel ions and zinc ions. However, the invention is not suitable for treating alkaline electroplating wastewater containing a large amount of complexing agent such as EDTA.
Therefore, how to provide a method for treating alkaline zinc-nickel alloy electroplating wastewater, which simplifies the treatment process, improves the treatment speed, reduces the treatment cost, is particularly suitable for treating electroplating wastewater rich in EDTA complexing agent, and becomes a problem to be solved urgently by technical personnel in the field at present.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a method for treating alkaline zinc-nickel alloy electroplating wastewater, which simplifies the treatment process, improves the treatment speed and reduces the treatment cost.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a method for treating alkaline zinc-nickel alloy electroplating wastewater, which comprises the following steps:
(1) mixing the acid solution with the electroplating wastewater to adjust the pH of the electroplating wastewater to 2.5 or less, which may be, for example, 0.1, 0.3, 0.5, 0.7, 0.9, 1.1, 1.3, 1.5, 1.7, 1.9, 2.1, 2.3 or 2.5, but is not limited to the values listed, and other values not listed in the range of values are also applicable;
(2) and (2) removing zinc ions and nickel ions in the electroplating wastewater obtained in the step (1) by using an ion exchange method.
Compared with the invention, the traditional treatment method is to remove zinc ions and nickel ions in the electroplating wastewater by a chemical precipitation method in an alkaline solution system, however, for the electroplating wastewater rich in ethylenediaminetetraacetic acid (EDTA) complexing agent, the zinc ions and the nickel ions are easy to keep stable and are difficult to reach the discharge standard.
In the invention, the pH value of the original alkaline electroplating wastewater is adjusted to be 2.5 or below in the step (1) by adopting a mode of mixing an acid solution and the electroplating wastewater, so that the complexing capability of an EDTA complexing agent in the electroplating wastewater is reduced, and the adverse effect of the complexing agent on the adsorption performance of a subsequently used cation exchange resin is further weakened.
Preferably, the acid solution in step (1) includes any one of a sulfuric acid solution, a hydrochloric acid solution or a nitric acid solution or a combination of at least two of them, and typical but non-limiting combinations include a sulfuric acid solution and a hydrochloric acid solution, a hydrochloric acid solution and a nitric acid solution, a sulfuric acid solution and a nitric acid solution, or a sulfuric acid solution, a hydrochloric acid solution and a nitric acid solution, and further preferably a sulfuric acid solution.
Preferably, the acid solution of step (1) has a concentration of 30 to 60 wt.%, and may be, for example, 30 wt.%, 35 wt.%, 40 wt.%, 45 wt.%, 50 wt.%, 55 wt.% or 60 wt.%, but is not limited to the recited values, and other values not recited within the range of values are equally applicable.
In the invention, the acid solution in the step (1) can be an industrial-grade sulfuric acid solution, so that the treatment cost is reduced.
Preferably, the electroplating wastewater obtained in the step (1) is allowed to stand still for 10-30min between the step (1) and the step (2), for example, 10min, 12min, 14min, 16min, 18min, 20min, 22min, 24min, 26min, 28min or 30min, but not limited to the enumerated values, and other non-enumerated values in the numerical range are also applicable.
Preferably, the ion exchange method in the step (2) is specifically: and (2) introducing the electroplating wastewater obtained in the step (1) into an ion exchange column, and neutralizing and discharging the effluent after detecting that the contents of zinc ions and nickel ions reach the standard.
In the invention, the standard reaching the standard is the emission standard of GB21900-2008 'electroplating pollutant emission standard', namely the emission standard of zinc ions is not higher than 1.0mg/L, and the emission standard of nickel ions is not higher than 0.1 mg/L.
In the present invention, the method for detecting the content of zinc ions and nickel ions is to use flame atomic absorption or inductively coupled plasma emission spectrometer for measurement, as long as the purpose of detecting the content of zinc ions and nickel ions in water can be achieved, and therefore, the method is not particularly limited herein.
In the invention, the neutralization is to neutralize the pH value of the effluent water by alkali liquor which is 7 +/-0.5, wherein the alkali liquor can be any one or the combination of at least two of sodium hydroxide solution, sodium carbonate solution or sodium bicarbonate solution.
Preferably, the resin packed in the ion exchange column comprises a cation exchange resin.
Preferably, the cation exchange resin comprises a strong acid cation exchange resin, which may be, for example, any one of or a combination of at least two of type 001 × 7(732), type 001 × 4(734), or type D001.
Preferably, the ion exchange column comprises two columns or three columns which are connected in series, effluent of each column needs to be detected, and when the detection shows that the content of zinc ions and/or nickel ions in effluent of one column exceeds 0.5mg/L, the feeding of electroplating wastewater into the one column is stopped, and resin filled in the one column is subjected to regeneration treatment.
In the invention, the resin filled in one column can be reused for treating electroplating wastewater after regeneration treatment, the desorption performance can still be kept at a good level, and the treatment cost is saved.
Preferably, the regeneration liquid used for the regeneration treatment comprises a sulfuric acid solution having a concentration of 3 to 8 wt.%, for example 3 wt.%, 4 wt.%, 5 wt.%, 6 wt.%, 7 wt.% or 8 wt.%, but is not limited to the recited values, and other values not recited within this range are equally applicable.
Preferably, the volume of the regenerating liquid is 3 to 5 times, for example, 3 times, 3.2 times, 3.4 times, 3.6 times, 3.8 times, 4 times, 4.2 times, 4.4 times, 4.6 times, 4.8 times, or 5 times, the volume of the resin packed in the certain column, but is not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the regeneration liquid after the regeneration treatment is subjected to neutralization and precipitation treatment to obtain the zinc-nickel-containing sludge with high concentration.
In the invention, the neutralization and precipitation treatment is to neutralize the regeneration liquid with alkali liquor with the pH value of 7 +/-0.5, wherein the alkali liquor can be any one or the combination of at least two of sodium hydroxide solution, sodium carbonate solution or sodium bicarbonate solution. The high-concentration zinc-nickel-containing sludge is sludge with zinc content and/or nickel content exceeding 20 wt%, and the high-concentration zinc-nickel-containing sludge can be subsequently disposed or sold.
Preferably, the ion exchange column has a height to diameter ratio of (2.3 to 3.5):1, and may be, for example, 2.3:1, 2.4:1, 2.5:1, 2.6:1, 2.7:1, 2.8:1, 2.9:1, 3:1, 3.1:1, 3.2:1, 3.3:1, 3.4:1 or 3.5:1, but is not limited to the recited values, and other values not recited in this range of values are equally applicable.
Preferably, the flow rate of the electroplating wastewater to the ion exchange column is 5-15 times volume/hour, such as 5 times volume/hour, 7 times volume/hour, 9 times volume/hour, 11 times volume/hour, 13 times volume/hour or 15 times volume/hour, but not limited to the values listed, and other values not listed in the range of the values are also applicable.
In the invention, the overflowing speed of the electroplating wastewater introduced into the ion exchange column is based on the volume of the resin filled in the ion exchange column, namely the overflowing speed of 5-15 times of volume/hour is specifically that the overflowing volume of the electroplating wastewater per hour is 5-15 times of the volume of the resin filled in the ion exchange column.
As a preferred technical solution of the present invention, the processing method includes the steps of:
(1) mixing 30-60 wt% sulfuric acid solution with electroplating wastewater, adjusting pH of the electroplating wastewater to be less than or equal to 2.5, and standing the obtained electroplating wastewater for 10-30 min;
(2) introducing the electroplating wastewater obtained in the step (1) into an ion exchange column with the height-diameter ratio of (2.3-3.5):1 and filled with strong acid cation exchange resin at the overflow speed of 5-15 times volume/hour, neutralizing and discharging the effluent after the contents of zinc ions and nickel ions reach the standard through detection; the ion exchange column comprises two columns or three columns which are connected in series, effluent of each column needs to be detected, when the content of zinc ions and/or nickel ions in effluent of one column exceeds 0.5mg/L, the introduction of electroplating wastewater into the one column is stopped, and resin filled in the one column is subjected to regeneration treatment; the regeneration liquid used for the regeneration treatment comprises a sulfuric acid solution with the concentration of 3-8 wt%, and the volume of the sulfuric acid solution is 3-5 times of the volume of the resin filled in a certain column; and carrying out neutralization and precipitation treatment on the regenerated sulfuric acid solution to obtain the high-concentration zinc-nickel-containing sludge.
Compared with the prior art, the invention has the beneficial effects that:
(1) compared with the traditional treatment method, the treatment method of the alkaline zinc-nickel alloy electroplating wastewater provided by the invention creatively adopts a mode of mixing an acid solution and the electroplating wastewater to adjust the pH value of the original alkaline electroplating wastewater to be 2.5 or below, reduces the complexing ability of an EDTA complexing agent in the electroplating wastewater, further weakens the adverse effect of the complexing agent on the adsorption property of a subsequently used cation exchange resin, and is particularly suitable for treating the electroplating wastewater rich in the EDTA complexing agent;
(2) the treatment method provided by the invention simplifies the treatment process, improves the treatment speed, reduces the treatment cost, reduces the concentration of zinc ions in the electroplating wastewater to 0.1mg/L at the lowest, and reduces the concentration of nickel ions to 0.05mg/L at the lowest, which all reach the discharge standard of GB 21900-;
(3) the treatment method provided by the invention obtains the sludge with the zinc content and/or the nickel content of more than 20 wt%, and the high-concentration sludge containing zinc and nickel can be sold for the outside, thereby improving the economic benefit.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments.
Example 1
The embodiment provides a method for treating alkaline zinc-nickel alloy electroplating wastewater, which comprises the following steps:
(1) mixing industrial-grade sulfuric acid solution with the concentration of 45 wt% with electroplating wastewater, adjusting the pH value of the electroplating wastewater to be 2, and standing the obtained electroplating wastewater for 20 min;
(2) introducing the electroplating wastewater obtained in the step (1) into an ion exchange column with a height-diameter ratio of 3:1 and filled with a 001 × 7(732) type strong-acid cation exchange resin at an overflow speed of 10 times of volume/hour, detecting the contents of zinc ions and nickel ions in effluent to reach the standard, neutralizing the effluent with a sodium hydroxide solution until the pH value is 7, and discharging the neutralized effluent; the ion exchange column is formed by connecting two columns in series, effluent of each column needs to be detected, and when the content of zinc ions and/or nickel ions in effluent of a certain column exceeds 0.5mg/L, the introduction of electroplating wastewater into the certain column is stopped, and resin filled in the certain column is subjected to regeneration treatment; the regeneration liquid used for the regeneration treatment is a sulfuric acid solution with the concentration of 5 wt%, and the volume of the sulfuric acid solution is 4 times of the volume of the resin filled in a certain column; and (3) neutralizing and precipitating the regenerated sulfuric acid solution by using a sodium hydroxide solution until the pH value is 7 to obtain high-concentration zinc-nickel-containing sludge, and selling the sludge.
In the embodiment, the electroplating wastewater is alkaline zinc-nickel alloy electroplating water from an electroplating factory in Hubei, a sample is taken before treatment, the zinc ion content is determined to be 80mg/L and the nickel ion content is determined to be 15mg/L through flame atomic absorption, the EDTA content is determined to be 1000mg/L through a coordination titration method, and the pH value is 11; after treatment, a sample is tested to have the zinc ion content of 0.1mg/L and the nickel ion content of 0.05mg/L through flame atomic absorption, and the zinc ion content and the nickel ion content all reach the emission standard of GB21900-2008 'electroplating pollutant emission standard'.
Example 2
The embodiment provides a method for treating alkaline zinc-nickel alloy electroplating wastewater, which comprises the following steps:
(1) mixing an industrial-grade sulfuric acid solution with the concentration of 30 wt% with electroplating wastewater, adjusting the pH value of the electroplating wastewater to be 2.5, and standing the obtained electroplating wastewater for 30 min;
(2) introducing the electroplating wastewater obtained in the step (1) into an ion exchange column which has a height-diameter ratio of 2.3:1 and is filled with a 001 × 4(734) type strong-acid cation exchange resin at an overflow speed of 5 times of volume/hour, detecting that the contents of zinc ions and nickel ions reach the standard, neutralizing the effluent by using a sodium carbonate solution until the pH value reaches 6.5, and discharging; the ion exchange columns are connected in series, effluent of each column needs to be detected, when the content of zinc ions and/or nickel ions in effluent of a certain column exceeds 0.5mg/L, the introduction of electroplating wastewater into the certain column is stopped, and resin filled in the certain column is subjected to regeneration treatment; the regeneration liquid used for the regeneration treatment is a sulfuric acid solution with the concentration of 3 wt%, and the volume of the sulfuric acid solution is 5 times of the volume of the resin filled in a certain column; and (3) neutralizing and precipitating the regenerated sulfuric acid solution by using a sodium carbonate solution until the pH value is 7.5 to obtain high-concentration zinc-nickel-containing sludge, and selling the sludge to the outside.
In this embodiment, the electroplating wastewater was obtained from chemical copper plating water of an electronics factory in suzhou, and before treatment, a sample was taken, and the content of zinc ions was measured by flame atomic absorption to be 70mg/L and the content of nickel ions to be 12mg/L, and the content of EDTA was measured by coordination titration to be 1500mg/L, and the pH was 12; after treatment, a sample is tested to have the zinc ion content of 0.15mg/L and the nickel ion content of 0.08mg/L through flame atomic absorption, and the zinc ion content and the nickel ion content both reach the emission standard of GB 21900-.
Example 3
The embodiment provides a method for treating alkaline zinc-nickel alloy electroplating wastewater, which comprises the following steps:
(1) mixing an industrial-grade sulfuric acid solution with the concentration of 60 wt% with electroplating wastewater, adjusting the pH value of the electroplating wastewater to 1, and standing the obtained electroplating wastewater for 10 min;
(2) introducing the electroplating wastewater obtained in the step (1) into an ion exchange column with a height-diameter ratio of 3.5:1 and filled with D001 type strong-acid cation exchange resin at an overflow speed of 15 times volume/hour, detecting the contents of zinc ions and nickel ions in the effluent to reach the standard, neutralizing the effluent by using a sodium bicarbonate solution until the pH value is 7.5, and discharging the neutralized effluent; the ion exchange column is formed by connecting two columns in series, effluent of each column needs to be detected, and when the content of zinc ions and/or nickel ions in effluent of a certain column exceeds 0.5mg/L, the introduction of electroplating wastewater into the certain column is stopped, and resin filled in the certain column is subjected to regeneration treatment; the regeneration liquid used for the regeneration treatment is a sulfuric acid solution with the concentration of 8 wt%, and the volume of the sulfuric acid solution is 3 times of the volume of the resin filled in a certain column; and (3) neutralizing and precipitating the regenerated sulfuric acid solution by using a sodium bicarbonate solution until the pH value is 6.5 to obtain high-concentration zinc-nickel-containing sludge, and selling the sludge to the outside.
In the embodiment, the electroplating wastewater is alkaline zinc-nickel alloy electroplating water from a certain electroplating plant in Henan, the zinc ion content is 90mg/L and the nickel ion content is 18mg/L by flame atomic absorption, the EDTA content is 1800mg/L by a coordination titration method, and the pH value is 13; after treatment, a sample is tested to have the zinc ion content of 0.2mg/L and the nickel ion content of 0.09mg/L through flame atomic absorption, and the zinc ion content and the nickel ion content all reach the emission standard of GB21900-2008 'electroplating pollutant emission standard'.
Example 4
This example provides a method for treating alkaline zinc-nickel alloy electroplating wastewater, which is similar to example 1 except that the strongly acidic cation exchange resin of type 001 × 7(732) in step (2) is replaced by a weakly acidic cation exchange resin of type D113, and therefore, the following description is omitted.
In the embodiment, the electroplating wastewater is alkaline zinc-nickel alloy electroplating water from an electroplating factory in Hubei, a sample is taken before treatment, the zinc ion content is determined to be 80mg/L and the nickel ion content is determined to be 15mg/L through flame atomic absorption, the EDTA content is determined to be 1000mg/L through a coordination titration method, and the pH value is 11; after treatment, a sample is tested to have the zinc ion content of 0.6mg/L and the nickel ion content of 0.09mg/L through flame atomic absorption, and the zinc ion content and the nickel ion content all reach the emission standard of GB21900-2008 'electroplating pollutant emission standard'.
Comparative example 1
This comparative example provides a method for treating alkaline zinc-nickel alloy electroplating wastewater, which is the same as example 1 except that the pH of the electroplating wastewater is adjusted to 2 and 3 in step (1), and thus, the details are not repeated herein.
In the comparative example, the electroplating wastewater is alkaline zinc-nickel alloy electroplating water from an electroplating factory in Hubei, a sample is taken before treatment, the zinc ion content is determined to be 80mg/L and the nickel ion content is determined to be 15mg/L through flame atomic absorption, the EDTA content is determined to be 1000mg/L through a coordination titration method, and the pH value is 11; after treatment, a sample is tested to have the zinc ion content of 0.8mg/L and the nickel ion content of 0.11mg/L through flame atomic absorption, and the nickel ion content does not reach the emission standard of GB 21900-.
Comparative example 2
The comparative example provides a treatment method of alkaline zinc-nickel alloy electroplating wastewater, which comprises the following specific steps: introducing the electroplating wastewater into an ion exchange column which has a height-diameter ratio of 3:1 and is filled with a 001 × 7(732) type strongly-acidic cation exchange resin at an overflow speed of 10 times of volume/hour, detecting the content of zinc ions and nickel ions in effluent, neutralizing the effluent by using a sodium hydroxide solution until the pH value is 7, and discharging the effluent; the ion exchange column is formed by connecting two columns in series, effluent of each column needs to be detected, and when the content of zinc ions and/or nickel ions in effluent of a certain column exceeds 0.5mg/L, the introduction of electroplating wastewater into the certain column is stopped, and resin filled in the certain column is subjected to regeneration treatment; the regeneration liquid used for the regeneration treatment is a sulfuric acid solution with the concentration of 5 wt%, and the volume of the sulfuric acid solution is 4 times of the volume of the resin filled in a certain column; and (3) neutralizing and precipitating the regenerated sulfuric acid solution by using a sodium hydroxide solution until the pH value is 7 to obtain high-concentration zinc-nickel-containing sludge, and selling the sludge.
In the comparative example, the electroplating wastewater is alkaline zinc-nickel alloy electroplating water from an electroplating factory in Hubei, a sample is taken before treatment, the zinc ion content is determined to be 80mg/L and the nickel ion content is determined to be 15mg/L through flame atomic absorption, the EDTA content is determined to be 1000mg/L through a coordination titration method, and the pH value is 11; after treatment, a sample is tested to have the zinc ion content of 1.2mg/L and the nickel ion content of 0.15mg/L through flame atomic absorption, and the zinc ion content and the nickel ion content do not reach the discharge standard of GB21900-2008 'discharge Standard of electroplating pollutants'.
The specific process of determining the EDTA content by the coordination titration method adopted in the examples 1-4 and the comparative examples 1-2 is as follows: firstly, preparing the electroplating wastewater into a sample solution with the pH value of 12 by using a sodium hydroxide solution, taking acid chrome blue K and naphthol green as mixed indicators, and then analyzing pure CaCO3The prepared solution titrates the sample solution, and the titration end point is determined when the solution changes from purple red to blue green.
Compared with the traditional treatment method, the treatment method for the alkaline zinc-nickel alloy electroplating wastewater provided by the invention innovatively adjusts the pH value of the original alkaline electroplating wastewater to be 2.5 or below by adopting a mixed acid solution and electroplating wastewater mode, reduces the complexing ability of the EDTA complexing agent in the electroplating wastewater, further weakens the adverse effect of the complexing agent on the adsorption property of subsequently used cation exchange resin, and is particularly suitable for treating the electroplating wastewater rich in the EDTA complexing agent; the treatment method simplifies the treatment process, improves the treatment speed, reduces the treatment cost, reduces the concentration of zinc ions in the electroplating wastewater to be 0.1mg/L at the lowest, and reduces the concentration of nickel ions to be 0.05mg/L at the lowest, which all reach the discharge standard of GB 21900-; in addition, the treatment method obtains the sludge with the zinc content and/or the nickel content of more than 20 wt%, and the sludge with high concentration containing zinc and nickel can be sold for the outside, thereby improving the economic benefit.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are only exemplary embodiments of the present invention, and are not intended to limit the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The method for treating the alkaline zinc-nickel alloy electroplating wastewater is characterized by comprising the following steps of:
(1) mixing the acid solution with the electroplating wastewater, and adjusting the pH of the electroplating wastewater to be less than or equal to 2.5;
(2) and (2) removing zinc ions and nickel ions in the electroplating wastewater obtained in the step (1) by using an ion exchange method.
2. The treatment method according to claim 1, wherein the acid solution in step (1) comprises any one of a sulfuric acid solution, a hydrochloric acid solution or a nitric acid solution or a combination of at least two of them, and is preferably a sulfuric acid solution.
3. The process according to claim 1 or 2, wherein the concentration of the acid solution of step (1) is 30 to 60 wt%.
4. The treatment method according to any one of claims 1 to 3, wherein the step (1) and the step (2) are performed by standing the electroplating wastewater obtained in the step (1) for 10 to 30 min.
5. The process according to any one of claims 1 to 4, wherein the ion exchange process of step (2) is in particular: and (2) introducing the electroplating wastewater obtained in the step (1) into an ion exchange column, and neutralizing and discharging the effluent after detecting that the contents of zinc ions and nickel ions reach the standard.
6. The process of claim 5, wherein the resin packed in the ion exchange column comprises a cation exchange resin;
preferably, the cation exchange resin comprises a strong acid cation exchange resin.
7. The treatment method according to claim 5 or 6, wherein the ion exchange column comprises two columns or three columns which are connected in series, effluent of each column is detected, when the content of zinc ions and/or nickel ions in effluent of one column is detected to exceed 0.5mg/L, the feeding of electroplating wastewater into one column is stopped, and resin filled in one column is subjected to regeneration treatment.
8. The treatment method according to claim 7, wherein the regeneration liquid used for the regeneration treatment comprises a sulfuric acid solution, the concentration of which is 3 to 8 wt%;
preferably, the volume of the regenerating liquid is 3 to 5 times the volume of the resin packed in the certain column;
preferably, the regeneration liquid after the regeneration treatment is subjected to neutralization and precipitation treatment to obtain the zinc-nickel-containing sludge with high concentration.
9. The process according to any one of claims 5 to 8, wherein the ion exchange column has an aspect ratio (2.3 to 3.5): 1;
preferably, the overflowing speed of the electroplating wastewater which is introduced into the ion exchange column is 5-15 times of volume/hour.
10. The process according to any one of claims 1 to 9, characterized in that it comprises the following steps:
(1) mixing 30-60 wt% sulfuric acid solution with electroplating wastewater, adjusting pH of the electroplating wastewater to be less than or equal to 2.5, and standing the obtained electroplating wastewater for 10-30 min;
(2) introducing the electroplating wastewater obtained in the step (1) into an ion exchange column with the height-diameter ratio of (2.3-3.5):1 and filled with strong acid cation exchange resin at the overflow speed of 5-15 times volume/hour, neutralizing and discharging the effluent after the contents of zinc ions and nickel ions reach the standard through detection; the ion exchange column comprises two columns or three columns which are connected in series, effluent of each column needs to be detected, when the content of zinc ions and/or nickel ions in effluent of one column exceeds 0.5mg/L, the introduction of electroplating wastewater into the one column is stopped, and resin filled in the one column is subjected to regeneration treatment; the regeneration liquid used for the regeneration treatment comprises a sulfuric acid solution with the concentration of 3-8 wt%, and the volume of the sulfuric acid solution is 3-5 times of the volume of the resin filled in a certain column; and carrying out neutralization and precipitation treatment on the regenerated sulfuric acid solution to obtain the high-concentration zinc-nickel-containing sludge.
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